CN114395248A - Red phosphorus flame-retardant polyamide composite material and preparation method and application thereof - Google Patents
Red phosphorus flame-retardant polyamide composite material and preparation method and application thereof Download PDFInfo
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- CN114395248A CN114395248A CN202111599785.5A CN202111599785A CN114395248A CN 114395248 A CN114395248 A CN 114395248A CN 202111599785 A CN202111599785 A CN 202111599785A CN 114395248 A CN114395248 A CN 114395248A
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 239000003063 flame retardant Substances 0.000 title claims abstract description 73
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000004952 Polyamide Substances 0.000 title claims abstract description 40
- 229920002647 polyamide Polymers 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title description 7
- 239000003365 glass fiber Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- 239000004760 aramid Substances 0.000 claims abstract description 24
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract description 24
- 239000004953 Aliphatic polyamide Substances 0.000 claims abstract description 11
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920003231 aliphatic polyamide Polymers 0.000 claims abstract description 11
- 239000003963 antioxidant agent Substances 0.000 claims description 14
- 230000003078 antioxidant effect Effects 0.000 claims description 12
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 229920006121 Polyxylylene adipamide Polymers 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000003094 microcapsule Substances 0.000 claims description 3
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 238000006068 polycondensation reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 26
- 238000001746 injection moulding Methods 0.000 abstract description 7
- 238000011161 development Methods 0.000 abstract description 3
- 230000010354 integration Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000000835 fiber Substances 0.000 description 24
- 238000007667 floating Methods 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 19
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920006139 poly(hexamethylene adipamide-co-hexamethylene terephthalamide) Polymers 0.000 description 3
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000012747 synergistic agent Substances 0.000 description 2
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000010076 replication Effects 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003878 thermal aging Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K2003/026—Phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a red phosphorus flame-retardant polyamide composite material which comprises the following components in parts by weight: 20-70 parts of aliphatic polyamide resin; 5-20 parts of aromatic polyamide resin; 10-50 parts of glass fiber; 8-20 parts of red phosphorus master batch; 1-5 parts of a synergist. The red phosphorus flame-retardant polyamide composite material provided by the invention has the advantages that through the introduction of the aromatic polyamide with a special structure, the aromatic polyamide, the red phosphorus flame retardant and the synergist have a synergistic effect, the glow wire performance (the GWIT can reach 775 ℃) and the flame retardant performance (the UL 94V-0 flame retardant grade of 0.8 mm) of the material can be obviously improved, the higher mechanical strength and modulus are simultaneously kept, the appearance of an injection molding part is good, the use requirements of the electronic and electrical appliance industry on the material under the development trend of high current, thin wall, miniaturization and integration can be met, and the application of the red phosphorus flame-retardant polyamide composite material in the field of electronic and electrical appliances is further widened.
Description
Technical Field
The invention relates to the technical field of engineering plastics, in particular to a red phosphorus flame-retardant polyamide composite material and a preparation method and application thereof.
Background
The red phosphorus flame-retardant polyamide has the advantages of excellent flame-retardant property, mechanical property, low smoke, high cost performance, electrical property and the like, and is widely applied to the field of electronic appliances such as electric switches, connectors, low-voltage circuit breakers and the like. With the continuous iterative update of the technology, the electronic and electrical industry has a development trend of high current, thin wall, miniaturization and integration, which requires that the red phosphorus flame-retardant polyamide material has better flame retardant property and glow wire property.
In the prior art, the flame retardant property of the material is improved by increasing the dosage of the red phosphorus flame retardant or introducing a flame retardant synergist such as zinc borate, magnesium hydroxide or montmorillonite. However, the above-mentioned methods for improving the flame-retardant property have not been found to improve the glow-wire property of the material well.
Chinese patent CN106336658A discloses a red phosphorus flame-retardant PA66/POK alloy which has higher GWIT, but POK is easy to degrade, has poor thermal aging performance and poor processing matching property with PA66, is not suitable for industrial application and mostly stays in the research stage. The Chinese patent CN102702734A compounds PA66, PPE, red phosphorus master batch and glass fiber to prepare the red phosphorus flame-retardant nylon with high heat resistance and high glow wire, but the PPE has poor toughness and poor compatibility with PA66, can seriously reduce the notch impact property of the composite material, and in addition, the PPE has poor fluidity and can influence the injection molding appearance of the material. US patent US 4136154A adopts organic aluminum hypophosphite and red phosphorus master batch to synergistically retard PA66, which is a better scheme at present for industrialization, but organic aluminum hypophosphite has a large damage to the mechanical properties of the flame retardant polyamide compound, and the organic aluminum hypophosphite has poor thermal stability, and has a certain degradation in the injection molding process, resulting in excessive gas, causing phenomena of marking, scorching and gas trapping on the surface of a part, and seriously affecting the appearance of the material. Therefore, at present, certain technical difficulties still exist in how to efficiently improve the performance of the red phosphorus flame-retardant polyamide glow wire.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide the red phosphorus flame-retardant polyamide composite material which has excellent flame retardant property and glow wire property, and an injection molded part of the red phosphorus flame-retardant polyamide composite material has good appearance.
The invention also aims to provide a preparation method of the red phosphorus flame-retardant polyamide composite material.
The invention also aims to provide application of the red phosphorus flame-retardant polyamide composite material
The invention is realized by the following technical scheme:
the red phosphorus flame-retardant polyamide composite material comprises the following components in parts by weight:
20-70 parts of aliphatic polyamide resin;
5-20 parts of aromatic polyamide resin;
10-50 parts of glass fiber;
8-20 parts of a red phosphorus flame retardant;
1-5 parts of a synergist.
Preferably, the red phosphorus flame-retardant polyamide composite material comprises the following components in parts by weight:
30-60 parts of aliphatic polyamide resin;
5-15 parts of aromatic polyamide resin;
20-40 parts of glass fiber;
8-15 parts of a red phosphorus flame retardant;
1-2 parts of a synergist.
Preferably, the aliphatic polyamide resin is selected from one or more of PA6, PA56 and PA 66.
The aromatic polyamide resin is selected from one or more of polyamide formed by polycondensation of monomers with a structure shown in a formula (I);
wherein n is a positive integer of 4-10.
Preferably, the aromatic polyamide resin is selected from one or more of PA MXD6, PA MXD8, PA MXD10 and PA MXD 12; more preferably, the aromatic polyamide resin is selected from one or more of PA MXD6 or PA MXD 10.
According to the invention, through research, the aromatic polyamide formed by condensing m-xylylenediamine is introduced, the aromatic polyamide has better compatibility with aliphatic polyamide, the strength and the modulus of the material can be effectively improved, and the amine group of m-xylylenediamine reacts with red phosphorus, so that the carbon forming speed and the carbon forming quality of the material are improved under the combined action of the synergist, and the glow wire performance and the flame retardant property of the material are obviously improved; on the other hand, the aromatic polyamide can reduce the crystallization speed of the red phosphorus flame-retardant polyamide compound, so that the melt has enough time to coat the glass fiber and the replication mold, thereby effectively improving the appearance of an injection molded part.
The glass fiber is any one or more selected from E glass fiber, H glass fiber, R, S glass fiber, D glass fiber or C glass fiber; preferably, the glass fibers are selected from E glass fibers.
The red phosphorus flame retardant is selected from any one or more of red phosphorus or red phosphorus master batch; preferably, the red phosphorus flame retardant is selected from microcapsule-coated red phosphorus master batches.
The synergist is selected from one or more of zinc borate, magnesium hydroxide, aluminum hydroxide or montmorillonite; preferably, the synergist is selected from zinc borate.
According to the material performance requirement, the red phosphorus flame-retardant polyamide composite material also comprises 0.1-0.5 part of antioxidant in parts by weight.
The antioxidant is selected from one or more of hindered phenol antioxidant, hindered amine antioxidant or copper salt. The copper salt is a general name of a copper salt antioxidant in the technical field, mainly comes from basf, inorganic copper salt is widely applied in the current market, and organic copper salt is mainly used for improving CTI performance.
The type and source of the antioxidant are not particularly required, and the technical personnel can select the type of the antioxidant to be added according to the actual situation requirement.
The invention also provides a preparation method of the red phosphorus flame-retardant polyamide composite material, which comprises the following steps:
uniformly mixing the components except the glass fiber according to the proportion to obtain a mixture; and (3) feeding the mixture from a main feeding port, feeding the glass fiber side, performing melt blending extrusion, cooling and granulating to prepare the red phosphorus flame-retardant polyamide composite material.
Further preferably, the melt blending extrusion is performed by using a twin-screw extruder.
Preferably, the temperature of the twin-screw extruder is 80 to 280 ℃.
Preferably, the screw length-diameter ratio of the twin-screw extruder is (40-48): 1.
preferably, the rotation speed of the screw of the twin-screw extruder is 250-350 rpm.
The invention also provides application of the red phosphorus flame-retardant polyamide composite material in the field of electronic appliances. In particular, the preparation method can be used for preparing an electric appliance switch, a connector or a low-voltage circuit breaker.
The invention has the following beneficial effects:
the red phosphorus flame-retardant polyamide composite material provided by the invention has the advantages that through the introduction of the aromatic polyamide with a special structure, the aromatic polyamide, the red phosphorus flame retardant and the synergist have a synergistic effect, the glow wire performance (the GWIT can reach 775 ℃) and the flame retardant performance (the UL 94V-0 flame retardant grade of 0.8 mm) of the material can be obviously improved, the higher mechanical strength and modulus are simultaneously kept, the appearance of an injection molding part is good, the use requirements of the electronic and electrical appliance industry on the material under the development trend of high current, thin wall, miniaturization and integration can be met, and the application of the red phosphorus flame-retardant polyamide composite material in the field of electronic and electrical appliances is further widened.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
The raw materials used in the examples and comparative examples of the present invention are described below, but are not limited to these materials:
aliphatic polyamide resin 1: PA66, designation PA66 EP-158, Huafeng group;
aliphatic polyamide resin 2: PA6, trademark PA6 HY-2800, Sun chemical fibers Inc.;
aliphatic polyamide resin 3: PA56, designation 1270W, Kaiser Co., Ltd;
aromatic polyamide resin 1: PA MXD6, brand AP-250, Yinggu Limited;
aromatic polyamide resin 2: PA MXD10, Yinggu Co., Ltd;
polyamide resin PA 66/6T: brand C1504T, shandong wide whole boundless novelty limited;
polyamide resin PA 6T/6I: brand No. TI1207, shandong wide whole boundless new materials limited;
glass fiber 1: e glass fiber, mark ECS10-3.0-568H, China megalithic corporation;
glass fiber 2: s glass fiber, designation S-1 HM435TM, Taishan glass fiber Limited;
red phosphorus master batch: the microcapsule is coated with red phosphorus master batch with the brand number FR9950T, Tung Cheng Xin De Co Ltd;
the synergist comprises the following components: zinc borate, commercially available;
antioxidant: hindered phenol antioxidant 1098, commercially available.
The preparation methods of the red phosphorus flame-retardant polyamide composite materials of the examples and comparative examples:
uniformly mixing the components except the glass fiber according to the proportion to obtain a mixture; feeding the mixture from a main feeding port, feeding the glass fiber side, melting, blending and extruding the mixture by a double-screw extruder, cooling and granulating the mixture to prepare the red phosphorus flame-retardant polyamide composite material; wherein, the length-diameter ratio of the screw is 40: 1, the rotating speed of the screw is 300rpm, and the segmentation temperature is 80-270-250-240-210-230-250 ℃.
The related performance test method comprises the following steps:
(1) flame retardant property: carrying out flame retardant property test on the sample strip according to the relevant standard of UL 94-2013, wherein the thickness of the sample is 0.8 mm; the flame retardant property has great significance for electrical safety, and the UL94 flame retardant grade can meet the application requirement only when reaching V-0.
(2) Glow wire performance: the glow wire ignition temperature of the samples was tested according to IEC 60695-2-11-2014, with sample sizes of 100 x 2 mm.
(3) Tensile property: the tensile speed is 10mm/min according to the test of ISO 527-2-2012 standard;
(4) bending property: testing according to ISO 178-2010 standard, wherein the bending speed is 2 mm/min;
(5) notched izod impact strength: testing according to ISO 178-;
(6) crystallization property: testing according to ISO 11357-2018 standard, wherein the heating and cooling rates are 10K/min, the nitrogen atmosphere is adopted, and the crystallization rate is represented by the full width at half maximum of the crystallization peak; the larger the full width at half maximum of the crystallization peak, the slower the crystallization rate.
(7) Appearance: and (3) injection molding a color plate (84 × 54 × 2.0 mm), observing floating fibers on the surface of the color plate, and evaluating according to the condition of the floating fibers on the surface of the color plate, wherein the color plate is divided into 4 grades, namely no floating fibers, no obvious floating fibers (the number of the fiber-shaped protrusions is less than 5, the protrusions are shallow, the appearance of the surface of the color plate is not influenced), obvious floating fibers (the number of the fiber-shaped protrusions is about 5-10, the protrusions are high, only good appearance can be kept), and more floating fibers (the number of the protrusions on the surface of the color plate is more than 10, and the appearance of the surface of the color plate is already obviously influenced).
Table 1: EXAMPLES 1-8 proportions (in parts by weight) of the ingredients and the results of the associated Performance tests
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | |
| PA66 | 30 | 60 | 50 | 50 | 50 | 50 | ||
| PA6 | 50 | |||||||
| PA56 | 50 | |||||||
| PA MXD6 | 5 | 15 | 10 | 10 | 10 | 10 | ||
| PA MXD10 | 10 | 10 | ||||||
| Red phosphorus master batch | 8 | 15 | 12 | 12 | 12 | 12 | 12 | 12 |
| Glass fiber 1 | 40 | 20 | 25 | 25 | 25 | 25 | 25 | |
| Glass fiber 2 | 25 | |||||||
| Synergistic agent | 1 | 4 | 2 | 2 | 2 | 2 | 2 | 2 |
| Antioxidant agent | 0.1 | 0.5 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | / |
| Tensile strength/MPa | 189 | 139 | 145 | 138 | 141 | 137 | 148 | 142 |
| Flexural modulus/MPa | 11700 | 7902 | 8100 | 7600 | 7830 | 7730 | 8530 | 8040 |
| Notched impact strength/kJ/m2 | 10.8 | 6.4 | 6.8 | 7.0 | 7.2 | 6.9 | 7.8 | 6.6 |
| GWIT/℃ | 800 | 775 | 775 | 775 | 775 | 775 | 775 | 775 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 | V-0 |
| Appearance of the product | The floating fiber is not obvious | Without floating fiber | Without floating fiber | Without floating fiber | Without floating fiber | Without floating fiber | Without floating fiber | Without floating fiber |
Table 2: comparative examples 1-9 proportion of each component (by weight) and relevant performance test results
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | |
| PA66 | 50 | 50 | 50 | 50 | 50 | 50 | 50 | ||
| PA6 | 50 | ||||||||
| PA56 | 50 | ||||||||
| PA MXD6 | 2 | 10 | 35 | 10 | 10 | ||||
| PA MXD10 | 10 | ||||||||
| PA66/6T | 10 | ||||||||
| PA6T/6I | 10 | ||||||||
| Red phosphorus master batch | 12 | 12 | 12 | 12 | 12 | 6 | 22 | 12 | 12 |
| Glass fiber | 25 | 25 | 25 | 25 | 25 | 25 | 25 | 25 | 25 |
| Synergistic agent | 2 | 2 | 6 | 2 | 2 | 2 | 2 | 2 | |
| Antioxidant agent | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Tensile strength/MPa | 133 | 137 | 128 | 140 | 130 | 145 | 127 | 130 | 129 |
| Flexural modulus/MPa | 7210 | 7530 | 7810 | 7900 | 8700 | 7820 | 8100 | 7200 | 7100 |
| Notched impact strength/kJ/m2 | 6.7 | 6.7 | 4.3 | 7.2 | 4.1 | 6.9 | 6.1 | 6.8 | 6.6 |
| GWIT/℃ | 725 | 725 | 775 | 700 | 775 | 675 | 775 | 725 | 725 |
| Flame retardant rating | V-0 | V-0 | V-0 | V-1 | V-0 | V-2 | V-0 | V-0 | V-0 |
| Appearance of the product | Much floating fiber | Obvious floating fiber | Much floating fiber | Without floating fiber | Without floating fiber | Without floating fiber | Much floating fiber | Much floating fiber | Much floating fiber |
It can be seen from the above examples and comparative examples that the red phosphorus flame retardant polyamide composite prepared by introducing aromatic polyamide with a special structure, and performing synergistic action with the red phosphorus flame retardant and the synergist has excellent mechanical properties, flame retardancy and glow wire properties, and the injection molded part has good appearance.
Comparative example 1/2 compared with example 3 shows that the aromatic polyamide resin can significantly improve the mechanical properties, glow wire properties and appearance of the material; when the aromatic polyamide resin is not added or the addition amount is too small, the tensile strength, the flexural modulus and the notch impact strength of the material are lower, the glow wire performance of the material is not obviously improved, the GWIT only reaches 725 ℃, the surface of an injection molding part of the material is seriously floated, and the appearance is poor.
In comparative example 5, the aromatic polyamide resin was added in an excessive amount as compared with example 3, but the tensile strength and notched impact strength of the material were rather lowered.
Compared with the example 5, the comparative example 3 has the advantages that the mechanical property of the material is reduced due to the excessively high content of the zinc borate, and the appearance of an injection molded part is also influenced to a certain extent; the reason for this analysis is that excessive zinc borate causes poor flowability and thermal stability of the material, resulting in poor appearance of the injection-molded article.
Comparative example 4 compared to example 6, the material achieved a flame retardant rating of 0.8mmV-1 with a GWIT of only 700 ℃ without the addition of zinc borate.
Compared with the example 3, the red phosphorus master batch of the comparative example 6/7 has too little addition, the flame retardant property and glow wire property of the material are poor, the flame retardant property only reaches 0.8mmV-2 flame retardant grade, and GWIT only has 675 ℃; the addition amount of the red phosphorus master batch is too much, so that the mechanical property of the material is obviously reduced, and the appearance of an injection molding product is poor.
Compared with the example 3, the PA66/6T or PA6T/6I selected in the comparative example 8/9 has no good improvement effect on the mechanical property, the glow wire property and the appearance of the material.
Claims (11)
1. The red phosphorus flame-retardant polyamide composite material is characterized by comprising the following components in parts by weight:
20-70 parts of aliphatic polyamide resin;
5-20 parts of aromatic polyamide resin;
10-50 parts of glass fiber;
8-20 parts of a red phosphorus flame retardant;
1-5 parts of a synergist.
2. The red phosphorus flame-retardant polyamide composite material of claim 1, which comprises the following components in parts by weight:
30-60 parts of aliphatic polyamide resin;
5-15 parts of aromatic polyamide resin;
20-40 parts of glass fiber;
8-15 parts of a red phosphorus flame retardant;
1-2 parts of a synergist.
3. The red phosphorus flame retardant polyamide composite material according to claim 1, wherein the aliphatic polyamide resin is selected from any one or more of PA6, PA56 or PA 66.
4. The red phosphorus flame-retardant polyamide composite material according to claim 1, wherein the aromatic polyamide resin is one or more selected from polyamides obtained by polycondensation of monomers having a structure represented by formula (I);
wherein n is a positive integer of 4-10.
5. The red phosphorus flame retardant polyamide composite material according to claim 4, wherein the aromatic polyamide resin is selected from any one or more of PA MXD6, PA MXD8, PA MXD10 or PA MXD 12; preferably, the aromatic polyamide resin is selected from one or more of PA MXD6 or PA MXD 10.
6. The red phosphorus flame-retardant polyamide composite material according to claim 1, wherein the glass fiber is any one or more selected from E glass fiber, H glass fiber, R, S glass fiber, D glass fiber or C glass fiber; preferably, the glass fibers are selected from E glass fibers.
7. The red phosphorus flame-retardant polyamide composite material according to claim 1, wherein the synergist is selected from any one or more of zinc borate, magnesium hydroxide, aluminum hydroxide or montmorillonite; preferably, the synergist is selected from zinc borate.
8. The red phosphorus flame-retardant polyamide composite material according to claim 1, wherein the red phosphorus flame retardant is selected from any one or more of red phosphorus or red phosphorus master batch; preferably, the red phosphorus flame retardant is selected from microcapsule-coated red phosphorus master batches.
9. The red phosphorus flame-retardant polyamide composite material as claimed in claim 1, further comprising 0.1 to 0.5 parts by weight of an antioxidant; the antioxidant is selected from one or more of hindered phenol antioxidant, hindered amine antioxidant or copper salt.
10. The method for preparing a red phosphorus flame retardant polyamide composite material according to any one of claims 1 to 9, characterized by comprising the steps of:
uniformly mixing the components except the glass fiber according to the proportion to obtain a mixture; and (3) feeding the mixture from a main feeding port, feeding the glass fiber side, performing melt blending extrusion, cooling and granulating to prepare the red phosphorus flame-retardant polyamide composite material.
11. Use of the red phosphorus flame retardant polyamide composite material according to any of claims 1 to 9 in the field of electronics.
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| CN114702821A (en) * | 2022-05-13 | 2022-07-05 | 福建联畅网络科技有限公司 | High-flame-retardant PA66 composite material for railway leakage coaxial cable lifting appliance |
| CN116120740A (en) * | 2022-12-27 | 2023-05-16 | 金发科技股份有限公司 | Flame-retardant polyamide material, and preparation method and application thereof |
| CN116875044A (en) * | 2023-07-26 | 2023-10-13 | 中山海明中科新材料有限公司 | Composite reinforced flame-retardant nylon material for new energy automobile and preparation method thereof |
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| CN112194894A (en) * | 2020-09-29 | 2021-01-08 | 金发科技股份有限公司 | Halogen-free flame-retardant polyamide composite material and preparation method thereof |
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| CN114702821A (en) * | 2022-05-13 | 2022-07-05 | 福建联畅网络科技有限公司 | High-flame-retardant PA66 composite material for railway leakage coaxial cable lifting appliance |
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| CN116120740A (en) * | 2022-12-27 | 2023-05-16 | 金发科技股份有限公司 | Flame-retardant polyamide material, and preparation method and application thereof |
| CN116875044A (en) * | 2023-07-26 | 2023-10-13 | 中山海明中科新材料有限公司 | Composite reinforced flame-retardant nylon material for new energy automobile and preparation method thereof |
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